N-(1-萘基)-琥珀酰亚胺光谱性质与构象的计算机模拟

首次采用Materialsstudio软件中不同的交换-相关势能函数对N-(1-萘基)-琥珀酰亚胺进行密度泛函理论计算,通过与文献报道的B3LYP/6-311G**常规计算方法进行比较,以及MP2/6-311G**方法进行单点能计算,确认所采用方法计算N-(1-萘基)-琥珀酰亚胺分子最低能量构象更接近整个势能面的全局最小点;振动频率理论分析结果与N-(1-萘基)-琥珀酰亚胺化合物羰基振动双重分裂的红外光谱特征相吻合,表明红外光谱可以作为琥珀酰亚胺类化合物的重要表征方法;根据对N-(1-萘基)-琥珀酰亚胺、萘和萘胺的轨道分布和电荷密度进行理论分析,解释了N-(1-萘基)-琥珀酰亚胺化合物溶液的紫外和荧光的光谱特征,并进而可推断N-(1-萘基)-琥珀酰亚胺分子在溶液中的构象和理论计算得到的真空中最低能量构象相同,其二面角为94.995°。     

Rh-catalyzed π-facial selective intermolecular hydroacylation of norbornenes

Rh-catalyzed π-facial selective intermolecular hydroacylations of norbornenes with salicylaldehyde have been attained. In the reaction with norbornylene, the exo-hydroacylated product was produced because of steric hindrance. In the case of norbornadiene, the endo-product was obtained because of chelation effect. Lastly, because of chelation and remote substituent effects, the product formed in the reaction of 7-tert-butoxynorbornadiene was the endo,syn-product. Deuterium-labeling experiments revealed that the hydroacylation stereoselectively proceeded via endo- and exo-intermediates.     

[Ru(DMSO)4]Cl2 catalyzes the α-alkylation of ketones by alcohols

The electrophilic α-alkylation of ketones with alcohols was accomplished by a [Ru(DMSO)₄]Cl₂ catalyzed process, water being the only wasted material. The reaction can be successfully governed to produce either the expected ketones or their related alcohols only by changing the reaction conditions. When 2-aminobenzyl alcohol was used, a cyclization process took place to yield 2,3-disubstituted quinolines.     

Cationic Xylan Derivatives with High Degree of Functionalization

Xylan from birch wood was characterized regarding both the supramolecular structure (X-ray, CP/MAS ¹³C-NMR) and the sugar composition. The reaction of the birch wood xylan with 2,3-epoxypropyltrimethylammonium chloride in 1,2-dimethoxyethane as slurry medium yields water-soluble, cationic 2-hydroxypropyltrimethylammonium xylan derivatives with high degree of substitution (DS). The DS values up to 1.6 can be controlled by adjusting the molar ratio in a one step synthesis. The structure of the cationic xylan derivatives was confirmed by means of DEPT(135) NMR spectroscopy. Film forming properties of cationic xylan derivatives were investigated with SEM measurements.     

Transfer Thermodynamics of Protein in Denaturing and Stabilizing Media

Free energies of transfer (ΔG_t) of RibonucleaseA (RNaseA) from water to aqueous solutions of urea (4 M, 6 M and 8 M), a protein denaturing solvent as well as ΔG_t of RibonucleaseA, β‐Lactoglobulin, α‐Chymotripsin and ChymotrypsinogenA from water to aqueous glycerol (10%, 20%, 30% and 40%), a protein stabilizing solvent has been dissected into cavity term [ΔG_t(cav)] and interaction term [ΔG_t(int)]. The interaction free energy includes all types of interactions like hard‐soft, hydrogen bonding, electrostatic, etc. The cavity forming free energies have been calculated using the standard version of scaled particle theory (SPT) with well‐reported SPT parameters. It has been found that transfer free energies of cavity terms ΔG_t(cav) for native protein from water to urea‐water and water to aqueous glycerol follow almost opposite trends. This primarily indicates there may be some correlation between cavity creation energies and protein denaturing and stabilizing ability of a solvent. The results are in agreement with those obtained from preferential binding coefficient studies in these media.     

Structural relaxation of Ti40Zr25Ni8Cu9Be18 bulk metallic glass

Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈ bulk metallic glass has a unique quenched-in nuclei/amorphous matrix structure. The crystallization of quenched-in nuclei, when the experimental isothermal annealing time is within its incubation time, may not disturb the enthalpy relaxation, which makes it have the accordingly common enthalpy relaxation behavior with amorphous materials. The alloy's annealing time dependence of recovery enthalpy follows a stretched exponential function with the mean relaxation time obeying an Arrhenius law. The equilibrium recovery enthalpy ΔH_T^eq, mean relaxation time τ and stretching exponent β are all dependent on the annealing temperature, and generally, a higher annealing temperature comes with a lower value of ΔH_T^eq, τ and a higher value of β. Two parameters, β_g and τ_g, representing the stretching exponent and the mean structural relaxation time at the calorimetric glass transition temperature, respectively, are correlated with glass forming ability and thermal stability, respectively. For Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈ BMG, the high value of β_g, which is much higher than 0.84 and approaches unity, reveals its good glass forming ability, while, on the other hand, the low value of τ_g indicates a worse thermal stability compared with typical BMGs.     

Application of electromagnetic processing for development of high-performance sintered powder metal parts

Electromagnetic processing was used to study the effects of electro-magneto forming on the dimensional control and thermal stability of sintered powder metal (PM) parts. The investigation was carried out on sinter-hardened, low chromium-molybdenum bainitic steel. The results show an increase in the microhardness of about 14% for the electromagnetic processed parts compared to the as-sintered parts. This was attributed to the 2% increase in the density, 17% and 29% reduction in the volume fraction of porosity and width of the bainitic lath, respectively, due to the electromagnetic processing. Dimensional characterization was carried out using a vertically aligned push-rod dilatometer. After four thermal cycles of heating and cooling, at a controlled rate of 5 °C/min to 1000 °C, the electromagnetic processed parts exhibited reduced dimensional change of about 44% lower than for the as-sintered parts. This is significantly important for applications that demand high dimensional tolerance and performance, especially at elevated temperatures.     

FAST ACCURATE PREDICTION OF BLANK SHAPE IN SHEET METAL FORMING

By using the Finite Element Inverse Approach based on the Hill quadratic anisotrop-ically yield criterion and the quadrilateral element, a fast analyzing software-FASTAMP for the sheet metal forming is developed. The blank shapes of three typical stampings are simulated and compared with numerical results given by the AUTOFORM software and experimental results, respectively. The comparison shows that the FASTAMP can predict blank shape and strain distribution of the stamping more precisely and quickly than those given by the traditional methods and the AUTOFORM.     

Direct Numerical Simulations of Premixed Turbulent Flames with Reduced Chemistry: Validation and Flamelet Analysis

Direct numerical simulation is a very powerful tool to evaluate the validity of new models and theories for turbulent combustion. In this paper, direct numerical simulations of spherically expanding premixed turbulent flames in the thin reaction zone regime and in the broken reaction zone regime are performed. The flamelet-generated manifold method is used in order to deal with detailed reaction kinetics. The computational results are analyzed by using an extended flame stretch theory. It is investigated whether this theory is able to describe the influence of flame stretch and curvature on the local burning velocity of the flame. It is found that if the full profiles of flame stretch and curvature through the flame front are included in the theory, the local mass burning rate is well predicted. The influence of several approximations, which are used in other existing theories, is studied. When flame stretch is assumed constant through the flame front or when curvature of the flame front is neglected, the theory fails to predict the local mass burning rate. The influence of using a reduced chemistry model is investigated by comparing flamelet simulations with reduced and detailed chemistry.     

The explicit representation to the principal rotation angle and the principal rotation axis

By using Cayley-Hamilton theorem, two kinds of explicit representation for the rotation tensor are proposed. One contains the lower powers of deformation gradient, by which the formula of the principal rotation angle and the explicit representation of principal axis are obtained; the other, a high efficient method to obtain the rotation tensor, does not contain the complicated coefficients and uses few variables. Some properties about the principal rotation angle and the principal rotation axis are obtained.